Beiträge zur Chemie der Pyrrolpigmente, 38. Mitt.: Zur Assoziation von Gallenpigmenten

The long standing problem of solvent dependent absorption spectra of certain bile pigments such as bilirubindimethylester has been solved by measurement of molecular masses by means of vapour pressure osmometry. Using this method and the investigation of the concentration and temperature dependence of the absorption spectra on several model compounds an association equilibrium for pigments of the rubinoid structural type could be confirmed. Moreover the optical properties of the coexisting species and the corresponding equilibrium constants could be deduced by spectroscopic techniques. Verdinoid pigments lacking free carboxylic functions on the other hand tend to be monomeric in solution. A heteroassociated species involving equimolar amounts of a verdinoid and a rubinoid pigment could be verified existing on adsorbents like silicagel.

37. Mitt.:Falk, H., Thirring, K., Tetrahedron, im Druck.     

Intramolecular Diels-Alder reactions: Construction of aza- and diaza-steroid type skeletons

The preparation of 2-(4-phenyl)butadienyl-piperidine 5 is described. An intramolecular Diels-Alder reaction of the intermediately formed fumaramide thereof produces stereoselectively the tricyclic lactam 6 . Its structure, as well as the configurational relationship of its 5 asymmetric centers, is corroborated on the basis of the NMR.-data. Cycloacylation of the thermodynamically stable precursors 13 and 20 leads to pentacyclic aza- or diaza-steroid type skeletons. Their structures ( 14, 16 , and 21 ) and in particular their relative configurations are elaborated. A few qualitative kinetic aspects of this intramolecular (4+2)-cycloaddition are presented.     

Chemie der Pleuromutiline, 10. Mitt.: 1,2-Transposition der Carbonylfunktion im Cyclopentanonteil des tricyclischen Gerüstes

2-Hydroxy-19,20-dihydropleuromutilin (10) undergoes a stereospecific ketolisomerisation when treated with base under phase/transfer conditions (11, 12). The subsequent reductive elimination of the 3-acetoxygroup afforded mutilin with a 1,2-transposed ketofunction (13).

     

Unitary transformation treatment of a single hole in an Ising antiferromagnet

The behavior of a single hole in a two-dimensional Ising antiferromagnet (t-J ^z model), is studied in the generalized Dyson-Maleev representation, where the spins are mapped on boson operators and the hole is described as a spinless fermion. The formal similarity with Fröhlich's polaron Hamiltonian suggests that thet-J ^z model can be approximately diagonalized by means of two successive unitary transformations, analogous to those used by Lee, Low, and Pines in their intermediate-coupling treatment of the polaron. Our approach yields an upper bound to the exact ground state energy, as well as the corresponding ground state eigenvector. Fork=0 our energy bound is remarkably close to the result of the self-consistent Born approximation over a wide range of the coupling parameter, which includes the range typically assumed for the high-T _c materials. The ground state eigenvector is used to calculate the spatial distribution of bosons (spin deviations) surrounding the hole. Here our results are qualitatively very similar to those obtained in previous work, showing that our ground state eigenvector accounts quite well for the small size of the “spin polaron” in thet-J ^z model.